High molal amine quaternary ammonium derivatives of alpha-halogen carboxy acid esters of oxyalkylated phenol-aldehyde resins



Patented Jan. 8, 1952 HIGH MOLAL AllIINE QUATERNARY AMMO- NIUM DERIVATIVES OF ALPHA-HALOGEN CARBOXY ACID ESTERS OF OXYALKYL- ATED PHENOL-ALDEHYDE RESIN S Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application December 13, 1948, Serial No. 65,089

8 Claims.

Said new compounds or compositions are qua-- ternary ammonium compounds obtained by reaction between a hydroxylated high molal amine selected from the class consisting of R=.o ,."rr in which R is an alkyl radical having at least 8 and and not more than 26 carbon atoms; R1 is an.

alkyl radical having not over 26 carbon atoms; R20 is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, butylene oxide,

r glycide and methylglycide radicals; n represents the numeral 1 to 6, and n" represents the numeral 1 to 3; and the ester of an alpha-halogen monocarboxylic acid having not over 6 carbon atoms and hydrophile hydroxylated synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide; and (B) an oxyalkylation-susceptible, fusible, organic ,solvent-soluble, water-insoluble, phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive towards said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula:

.;.;a;wmn hislexlh g ee bee we; having at least 4 and not more than 12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R10)n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be intro duced for each phenolic nucleus.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine dropletso'i' naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitute the continuous phase or the emulsion. This specific application is described and claimed in our co-pending application Serial No. 65,088, filed December 13, 1948, now Patent 2,542,004, granted February 20, 1951. The new products are useful as Wetting, detergent and leveling agents in the laundry, textile and dyeing industries, as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the notation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides; emulsifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

The esters of alpha-halogen monocarboxy acids with oxyalkylated phenol-aldehyde resins which are converted to the quaternary ammonium compounds of the invention are described in our Patent 2,542,004, granted February 20, 1951. The phenol-aldehyde resins and their oxyalkylation are described in our Patent 2,499,370, granted March 7, 1950. Reference is made to these patents for a description of the phenol-aldehyde resins used, their oxyalkylation and their conversion to alpha-halogen monocarboxy acid esters. For examples of phenol-aldehyde resins, reference is made to Examples 1a through 103a of Patent 2,499,370. For examples of the oxyalkylated resins, reference is made to tables at columns 31 through 46 of Patent 2,542,004. For examples of the alpha-halogen monocarboxy acid esters of theseoxyalkylated resins, reference is least one radical containing 8 to 22 carbon atoms and at least one hydroxyalkyl radical orthe equivalent, for instance, a hydroxyalkyl radical in which the alkyl carbon-atom chain is interrupted by an oxygen atom. There may be present a low molal alkyl radical such as a methyl radical. More specifically, the hydroxylated amines contemplated -may be indicatedrby the following formulae:

(RiOLwH an (R'zOLWH in which R'is an alkyl radical having at'least 8 V and not more than 26 carbon atoms; R1 may be the same as R, or may represent a low molal alkyl radical, such 'as'm'ethyl radical; R20 is an alkylene oxide radical selected from the class consisting of ethylene oxide, propylene oxide,

plified by'theprior formulae:

(ago) aninwhich R is an 'alkyl radical-having at least 8 and not more than -26'carbonatoms; Ri-may be the same as 1 3,, or may represent a-low molal alkyl radical, such as methyl -radical;-RzO is an alkylene oxide radical selected from the -class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide; -11. indicates the numeral 1 -to'6, andn' indicates the numeral 1 to 3.

As to the production of hydroxylated high molal amines of the kind above described, see- U. S. Patent No. 2,394,432, dated Februaryfi, 1946, to De Groote and Keiser, or U. S; Patent No. 2,329,699, dated September 21, 1943, to De Groote and Keiser. What is said hereinafter is substan- 1941, to De Groote and Keiser.

4 radical may occur as many as five times. Such hydroxylated high molal aminesare obtained by conventional "procedurain which a high molal primary or secondary amine is submitted to the action of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, and the like; The oxyalkylating agents employed'are the kind which contain 4 carbon atoms orle'ss in the hydrocarbon radical.

Our preferred cXyalkylating agent is ethylene oxide, due to its availability, comparatively low oost,"a1 1d"its increased reactivity, in comparison.

with other oxyalkylating agents.

As to patents which illustrate the oxyalkylation of high molal amines, reference is made to IS. Patent No; 2,233,383, dated February 25,

See Examples 2, 8 and' l4 in said De Groote and Keiser patent. See also U. S. Patent No. 1,970,578, dated August 21, 1934. to Schoeller-and Wittwer.

Amines ofthe kind enumerated, which are used as primary reactants for the manufacture of hydroxylated high molal primary or secondary amines, may be produced in various manners. They may be produced from naphthenic acids, resin acids, fatty acids, oxidized petroleum acids, or the like, by converting the acid into the ester, preferably the ethyl ester or the like, and then converting the ester into the alcohol. Such alcohols derived from various fatty acids, naphthenic acids, oxidized petroleum acids, resin acids, and the like, are available commercially and are em ployed in the manufacture of wetting agents or the like by sulfating or sulfonating such alcohols. Such high molal alcohols can be converted into the chlorides, and the chlorides reacted with ammonia or a primary or secondary amine to give amines of the type herein contemplated. If derived from higher fatty acids, such as stearic acid, the hydrocarbon chain is simply an alkyl radical. Naturally, if derived from an unsaturated fatty acid, such as oleic acid, the radical would represent an unsaturatedhydrocarbon radical. If derived from ricinoleic acid or some other hydroxy acid, such ashydroxystearic acid, one would have 1a hydroxylated hydrocarbon radical.

In actual praetice,.=amines of the kind herein contemplated can be obtained in various ways.

Reference is made toa-number of patents which disclose or describe such amines, or the method of manufacturing the same. In some cases, obvious modifications will be required to produce amines of the kind contemplated, but such modifications would be evident to a skilled chemist, without further discussion. See the following patents: U. S. Patents Nos. 1,951,469, Bertsch,

tially as it appearsin verbatim formin the last aforementioned patent.

The amines employed for reaction, are-characterized by containingat least one group having a hydrocarbon radical, which, in turn, has at least 3 carbon atoms and may haveas manyas 26 carbon atoms, or even more. Such amineis or the hydroxylated type, by virtue of the presence of at least one hydroxy hydrocarbon radical, or similar radicals, in which the carbon-atom chain is i nte rrupted -atleast once by an; oxygen atom. Such ether linkages in the hydroxylated March 20; 1934;.-.-2,006,058, 01in, June 25, 1935; 2,033,866, Schrauth, March 10,1936; 2,074,380, Flett, March 23, 1937; 2,075,825, Nafash, April 6, 1937; 2,078,922, A'rnold, May 4, 1937; 2,091,105, Piggott, August 24, 1937; 2,108,147, Speer, February 15, 1938; 2,110,199, Carothers, March 8, 1938; 2,132,902, Lenher, October 11, 1938;

2,178,522, Ralston, October 31, 1938; British 359,001, Johnson, I. G. Farb. A. G. 1932; British 358,114, Carpma'eLI. -G.=Farb. A. G. 1932; See also Industrial and Engineering Chemistry, Industrial Edition, volume 32, No. 4 (1940), p.436.

In view of what has been said, it will be noted that the group introduced into the amine and derived at least hypothetically from'an acid, is really the carbon chain radical of the acyl group of the acid or hypothetical acid, along with what fwas at :least hypothetically the carbonyl carbon atom. For the sake of convenience. this radical will be renamed as a hydro'earb6nradicalism! it"is intended to include derivatives in "which'a 'hydrogenatom or a small'number of hydrogen atoms have been'replaced by the hydroxyl radical; for instance, the hydroxyhydrocarbon 'radiacid, hydrox'yst'earic acid,for"the"like; "and such hydroxyl groups are essentially.non fiinctional, in that they are not relied upon 'to'siipplypoints of cheniical activity They may; slightly decrease thehydrophobe characters: the "radical tosome degree; but this "cannot be significant, as "can be appreciated by referencetori'cinoleic acid. Since the carbon atom chain supplied to the amine by means of ric'inoleica'cid hasl8'carbon atoms, it would appear relatively "immaterial whether there waspresent one hydroxyl group or not. Thus, it is to be bor'n'ein mind that the use in the hereto appended claims of the word hyd'r'o'carbon is intended to include the hydroxy hydrocarbon type 'of the kind in which-the hydroxyl group doe's not materially reduc'e'the hydrophobe character of the hydrocarbon group, as, for example, the group or radical which would be obtained from -ricinolei'c acid.

Certain facts are obvious in the preparation of "the hydroxylated amines. If a secondary amine is employed as a primaryreactant, then obviously, only one hydroxylated radical can be introduced. On the other hand, if a primary amine is employed, then two hydroxylated radicals may be introduced by the use of ethylene oxide, or the like. Furthermore, the initial reaction with ethylene oxide'or the like "does -'not produce an ether linkage, whereas, subsequent reaction does. Where two high molal groups are present in an. amine, they neednot be the same. Furthermore;asecondary amine containingone high molal gr'oupand one low molal group might be employed. For instance, methyl oc'tylamine, ethyl octylamine, propyl octylamine, methyl decylamine, ethyl decylamine, propyl decylamine, etc. Our preference is to use primary amines -'as raw materials, rather "than secondary amines, and particularly, amines which have been derived from carboxy acids. For'instance, note the following: Octadec'enylamine, -cetylamine,

, 6 derived rro'm" napiitneme acids: amines derived "from octadecadiene 9,-11-acid-1; octadecylamin'e; amines derived from mixed unsaturated fatty acids, such assoyabean fat I acids; cottonseed oil fatty acids; linseed oil fatty'acids; =heptadecylamine, hexadecylamine; dodecylamine; decylamine, etc. I

Attention is also directed to the fact that suitable amines can be derived from oxidized wax acids. As to the natureof these acids, see U. S. Patent No. 2,242,837," dated May 20, 1941, to Shields. It "is well-known that certain varieties of such wax acids contain approximately 22-26 carbon atoms, Whereas, oxidized acids containing fewer carbon atoms'are also available. It is again desirable '"to" note "that'the high molal hydrocarbongroup joined wane amino nitrogen atom may be aliphatic, alicyclic, aryrer aralkyl in nature, as, for example,hydroxylatedamines obtained by the oxyalkylationof-naphthylamine or the like, and substituted naphthylaminessuch as alkylated naphthylamines. Attention is directed to the fact that the amines in which there is no aryl group directly joined to'theamino nitrogen atom, are comparatively basic in nature, i. e., the type which has previously been indicated as aliphatic, alicyclic,-or aralkyl. It is our preference to use thebasictype, i. e., wehave found hydroxylated high molal amines in which there is no aryl group directly joined to the amino nitrogen atom, tobe the most desirable type of reactant for producing the new composition of matter, particularly when it is employed as a demulsifying agent. 1

: From a commercialstandpoint wehave found that itis the most simple to purchase high molal primary or secondary-amines and to treat such primary amines with two or more moles, up-to a dozen moles, of alkylene oxide, particularlyethylene oxide or propylene oxide, or treat a -secondary amine with one to six moles of either ethylene oxide or propylene oxide. Since these :amines are highly basic, reaction takes, place in the conventional manner with exceeding. ease. We have simply used conventional procedure, and the reaction takes place-"without the slightest irregularity. The amines which we prefer to use are those sold by the Armour cheniical Division of Armour 8: Company, Chicago. lllinoisi ancl the following shows the composition and trade designationof those which we have subjected to oxyethylation and found entirely; satisfactory for the production of the quaternaryv derivatives herein destearylamine, ole'oamine, ricinoleoamine'; amines scribed;

Y a -Armourlrade Chemical I Formula Name octylamme omwnmomnm Q Armeen a. Decylarniness CHs(CH2)sCHzNHz; Armeen' l0. Do'decyla'mine CHs(OHa)iuCHzNH2 Ari'n'e'en i2. Tetrade'cylam CH3(CH2)lzCH2NHz Armeen l4, 1 Hexadecylamme CHaCHfluCHzNHz Armecn 16. octadecylaminen C OH2)15CH2NH2 Arm'ee'n 18 .Octadeeenylamine; -..OHa(OH:) 1 OH:OH-(GHZ)1OH Armeen 0. Coconut Oil Amine-"use"; I H Armeen C. -s'o' sbsnmmmenu Arms-ems.

randw'smme Arfiie'eh '1 Hydrogenated Tallow Amine {$2 Arm'en-"HT. secondary Oct'ylzififlnel. (CHa(CHa)oCH2gzNH Diarmen'8.- Secondary Decylamine.- (CHZ(OH2)8 CH2 2N Diarmeen-lo. Secondary Dodecylamiil CHa(CH2)inCH2)-2N Dlarriieje'nf l2 CHa( H2)12CH2)2NH Diar'meeh IQ. -(QHaECH2) g-QH2)2NH Diermeen 16 (CH; canton-01MB Dlsnfieen 18;. -(GHsQCHahCH-lOH-(G a We have also employed rosin amine sold under the trade name of Rosin Amine D," by the Hercules Powder Company, of Wilmington, Delaware. The main component of this particular amine is the folowing:

NH2--CH1 CH3 CH ca H, C H: S means the indicated ring is saturated. Formulae of preferred hydroxylated reactants are as follows:

' (CH3(CH.2) sCHz) 2N (CzHiOH) (CI-13(CH2) sCI-Iz) 2N(C2H4OH) (CH3 (CH2) CH2) 2N (C2H4OH) (CH3 (CH2) 12CH2) 2N(C2H4OH) (CH3 (CH2) 14CH2)2N(C2H4OH) (CH3 (CH2) isCHz) 2N(C2H4OH) (CH3 (CH2) 'zCH CH(CH2) 7CH2) 2N C2H4OH) Example 1d in which 'n, is 4 or 5 on the average, and R. is CH3(CH2)CH2 and x is 6 to 16. The secondary amine, as stated, had a molecular weight of 430, and the tertiary amine as employed, i. e., the oxyethylated derivative, had a molecular weight of 628.

The ester contained xylene, as previously described. Along with the tertiary amine there was invariably added a small amount of xylene, in each case equal in weight to of the tertiary amine. In the instant case this was 12.5 grams. A little xylene was lost during the subsequent reflux period. The experiments were conducted so that in the majority of cases the final product contained approximately xylene. If desired, this xylene could be eliminated by evaporation or vacuum distillation. In the use of the products for demulsification it is convenient to have the xylene present so as to give a non-viscous liquid which can be handled readily.

The two reactants were refluxed at the boilin point of xylene (approximately 140 C.) for 2 to 4'hours.

Tests in this kind of reaction have invariably indicated that the reaction was complete usually in less than 2 hours and sometimes in as little as 30 minutes. However, by way iofprecaution in this experiment, and in succeeding experiments, such time range of 2 to 4 hours was employed. The final product, without eliminating the xylene, was a deep ambercolored liquid, readily water-emulsifiable. The

product, after the reaction was completed, contained 38.4% xylene.

Example 211 The procedure employed was identical with that in Example 1d, except that 250 grams of the ester identified as 150 of Patent 2,542,004 were reacted with 68 grams of the tertiary amine describedspecifically under the heading of Example 1d. The product contained 38.4% xylene,

and its color and emulsifiability were substantially the same as in Example 1d.

Example 3d Example 4d The procedure employed was identical with that in Example 111, except that 400 grams of the ester identified as 140 of Patent 2,542,004, were reacted with 126 grams of the tertiary amine described specifically under the heading of Example 1d. The product contained 393% xylene, and its color and emulsifiability were substantially the same as in Example 1d.

Example 5d The procedure employed was identical with that in Example 1d, except that 400 grams of the ester identified as of Patent 2,542,004, were reacted with 156 grams of the tertiary aminedescribed specifically under the heading of Example 1d. The product contained 37.8%

xylene, and its color and emulsifiability were substantially the same as in Example 1d.

Example 6d The procedure employed was identical with that in Example 111, except that 400 grams of the ester identified as of Patent 2,542,004 were reacted with 126 grams of the tertiary amine described specifically under the heading of Example 1d. The product contained 38.2% xylene, and its color and emulsifiability were substantially the same as in Example 1d.

Example 7d Example 8d The procedure employed was identical with that in Example 1d, except that 400 grams of the ester identified as of Patent 2,542,004 were reacted with 178 grams of the tertiary amine described specifically under the heading of Ex- .aeena'ae ample. 1d. -The product. contained 43:3 xylene, and: its color .and.-.-emulsifiability .were substantially tlie .same:. as i inEXample 11d.

' Example 9d The procedure employed was identical with that inExample ld exceptthat400grams of-the I ester. identified .as 190 of Patent-2,542,004 were reacted with 128. grams of the tertiary amine idescribed specifically under the-headingof Example 1d. .The. product contained 37% xylene, and itscolor and emulsifiability weresubstantially the same asini-Exampleld.

Example' wd The procedure employed was identical with that in Example .ld, exceptthat' 400'gramsof the esteridentified as 180 of Patent 2,542,004 were reacted with'7 grams-of the tertiary. amine described specifically under'the heading of Ex- 'ampleld. The product contained'36.4% xylene,

and its color and: emulsifiability were substantially the same as in Example 1d.

Example 11d In this example, and in subsequent examples,

- other procedure was the's'ame'astthat employed in Example 1d, preceding. .Theiresulting product was deep amber in color, very water-soluble; and contained 40.8% xylene.

Example 12d .The procedureemployed. was the samevas that inExample 1d, except that 250 grams of theester identified as 150 of Patent 2,542,004 were reacted with 4'75 gramsof the tertiary aminer'described specifically under the heading of- Example lld; The product contained 41.8% xylene; itwas deep amber in color and very water-soluble.

Example 13d The procedure employed was the same as that in Example 111, except that 400 grams of the ester identified as 13c of Patent 2,542,004 were reacted with 108 grams of the tertiary amine described specifically under the heading of Example lid. The resulting product: contained 43.5% xylene, and its color and emulsifiabil-ity were about the same as in Example 11d.

Example 14d The procedure. employed was.. the:same ias -that inExample .1 d,. exceptthat 400 gramsioffthe ester Theiresulting itscolori and asrinaExamplelld.

The procedure employed; wast iii-Example 1d, exceptthatf400 grams of the ester identified as of Patent 2,542,004 were reacted with-109: grams of the I tertiary amine described specifically under the heading of Example-11d. The resulting product contained 41.6% xylene, and its color and emulsifiability were about the same as in Example 11d.

Example "1 6d The procedure employed was the same as that in Example 1d, except that 400 grams of the ester identified as ofPatent 2,542,004 were reacted with 87.5 grams of the tertiary amine described specifically under the heading of Example 11d. The resulting product contained 41% xylene, and its color and emulsifiability were-about the same as in Example 11d.

i Escample 17d The procedure employed was the'sam'eas that in Example-1d, exceptthat 400 grams of the''s'te'r identified'as 2c of 'Patent 2,542,004 were reacted with 146grams' of the'tertiary amine described specifically un'der the heading of Example 1111. Example 18d r The 'procedure employed was the same-as that in Example-1d, except that 400 grams of the ester identified as12c cfPatent 2,542,004 wer'ereacted with '124' grams of the tertiary amine described specifically under the heading of Example lid. The resulting product contained 47.6% xylene, and its'color and emulsifiability were aboutthe same-as in Example 11d.

' Example 19a The procedure employed was the same as that inExample'ld, except that 400 grams of the ester identified as 190 of Patent 2,542,004 werereacted with 89.5 grams of the tertiary amine described specifically under the heading of Example 11d. The resulting product contained 39.8% xylene, and its color and emulsifiabi-lity were about the same as in Example 1111.

Example 20d The procedure employed was the same as that in Example 1d,.except that 400 grams of the ester identified as of Patent 2,542,004 were reacted with 109 grams of the tertiary amine described specifically under the heading of Example 11d. The resulting product contained 40% xylene, and its color and emulsifiability were about the same as in Example 11d.

' Ea'ample 21d 'fThe procedure employed was the-same-as that in Example Je xcept that 400 gramsof-the ester identified "as'j20c df Patent 2,542,004 were reacted with 76 "grams o'fthe tertiary amine described specifically uhde'r'the heading of Example 1111. The" resulting. product contained" 39.7% xylene, and its color and emulsifiability were abofutthe same as inExamplelld. J

The procedure employed was'the same as that in Example 1d, except that 400 grams of the ester identified as 30 of Patent-2,542,004 were reacted with 93 grams of the tertiary amine described specifically under the heading of Example 1111. The resulting productcontained 39.4% xylene,

' and its color and eirfuls'ifiabilitywere about the same as in Example 11d.

' Having thus described our-invention, what we claim as new and desire to secure by Letters Patent is:

l. A quaternary ammonium compound obtained by reaction between a hydroxylated high molal amine selected from the class consisting of and not more than 26 carbon atoms; R1 is an alkyl radical having not over 26 carbon atoms;

, R20 is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, butylene oxide, glycide and methylglycide radicals; n represents the numerals 1 to 6, and n" represents the numeral l to 3; and an ester in which the acyl radical is that of an alpha-halogen monocarboxylic acid having not over 6 carbon atoms and composed of carbon, hydrogen, oxygen and halogen and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyallq'lation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive towards said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyalkylated resin being characterized by the introduction into the resin molecule at all) in which R is-an alkyl radical having at least 8 and not more than 26 carbon atoms; R1 is an alkyl radical having not over 26 carbon atoms; R20 is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, butylene oxide, glycide and methylglycide radicals; n represents the numeral 1 to 6, and n" represents the numeral l to 3; and a chloroacetate of certain hydrophile synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butyleneoxide, glycide, and methylglycide, and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenolaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive to-' wards said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula:

in which R is a hydrocarbon radical having at least '4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyalkylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (R10)n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of the ultimate quaternary ammonium compound as well as the oxyalkylated resin in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

3. A quaternary ammonium compound obtained by reaction between a hydroxylated high molal amine selected from the class consisting of in which R is an alkyl radical having at least 8 and not more than 26 carbon atoms; R1 is an alkyl radical having not over 26 carbon atoms;

R20 is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, butylene oxide, glycide, and methylglycide radicals; n represents the numeral 1 to 6; and n" re resents the numeral 1 to 3; and a chloroacetate of certain hydrophile" polyhydric synthetic-products; said hydrophile synthetic products being oxyethylation, products or (fl) ethylene oxide, and (B) an oxyethylationsusceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol andan aldehyde having not over 8 carbon atoms and having one functional group reactive towards said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (021-140); wherein n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of the ultimate quaternary ammonium compound as well as the oxyethylated resin in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

4. A quaternary ammonium compound obtained by reaction between a hydroxylated high molal amine selected from the class consisting of in which R is an alkyl radical having at least 8 and not more than 26 carbon atoms; R1 is an alkyl radical having not over 26 carbon atoms; R20 is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, butylene oxide, glycide, and methylglycide radicals; n represents the numeral 1 to 6, and n" represents the numeral 'l to 3; and a chloroacetate of certain hydrophile synthetic products; said hydrophile and synthetic products being oxyethylation products of (A) ethylene oxide, and (B) an oxyethylationsusceptible, fusible, organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 7 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than,12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (C2H40)n; wherein n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of the ultimate quaternary ammonium compound as well as the oxyethylated resin in an equal weight of xylene are sumcient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

5.,The product of claim 4, wherein R is substituted in the para position.

6. The product of claim 4, wherein R is a butyl radical substituted in the para position.

7. The product of claim 4, wherein R is an amyl radical substituted in the para position.

8. The product of claim 4, wherein R is a nonyl radical substituted in the para position MELVIN DE GROOTE. BERNHARD KEISER.

REFERENCES CITED UNITED STATES PATENTS Name Date De Groote Mar. 7, 1950 Number 

1. A QUATERNARY AMMOUNIUM COMPOUND OBTAINED BY REACTION BETWEEN A HYDROXYLATED HIGH MOLAL AMINE SELECTED FROM THE CLASS CONSISTING OF 